Copper or copper alloy article comprising surface-modified polyester-based resin and manufacturing method

ABSTRACT

Disclosed is a copper alloy article including: a substrate 10 made of a copper alloy; a polyester-based resin body 40; and a compound layer 20 for bonding the substrate 10 and the polyester-based resin body 40, wherein the compound layer 20 contains; a compound having a nitrogen-containing functional group and a silanol group, and an alkane type amine-based silane coupling agent.

RELATED APPLICATIONS

This application is a Divisional of U.S. patent application Ser. No.16/072,597, filed on Jul. 25, 2018, which is a U.S. National PhaseApplication of International Patent Application No. PCT/JP2017/000855,filed Jan. 12, 2017, which claims priority to and the benefit ofJapanese Patent Application No. 2016-013477, filed on Jan. 27, 2016. Thecontents of these applications are hereby incorporated by reference intheir entireties.

TECHNICAL FIELD

The present disclosure relates to a copper alloy article including acopper alloy in which a polyester-based resin member is bonded to atleast a part of a surface thereof, and a polyester-based resin membersuitable for manufacturing a copper alloy article, and a manufacturingmethod thereof.

Copper alloys have widely been used in electric and electroniccomponents as rolled materials, expanded materials, foil materials andplating materials because of excellent electrical conductivity andthermal conductivity. Copper alloys are indispensable materials aswiring materials, and electronic circuit boards (printed wiring boards)in which a copper wiring and an insulating layer mainly made of a resinare composited are used in electronic devices. The printed wiring boardsinclude rigid printed wiring boards using, as the material of aninsulating layer, materials having no flexibility obtained byimpregnating a glass fiber with a resin material such as an epoxy resinand curing the resin material, and flexible printed wiring boards(hereinafter referred to FPC) using, as the material of an insulatinglayer, thin flexible resin materials such as a polyimide film and apolyester film.

In any printed board, there is a need to increase the bonding forcebetween the resin material and the copper wiring, and various techniqueshave been proposed. For example, there has been known a flexible copperclad laminate (FCCL) using, as the base material used for FPC, amaterial obtained by bonding a copper foil to one or both surfaces of aresin film. To improve the bonding strength between the resin film andthe copper foil, there has been used a method in which a surface of thecopper foil is roughened and an adhesive or a heated resin surface isadhered to irregularities of the roughened surface (anchor effect).

However, in high frequency signal, signal flows through a surface layerof the wiring due to the effect called the skin effect, so that if thesurface of the copper foil has irregularities, the transmission distancebecomes longer leading to increased transmission loss. Therefore, in thetransmission loss which is an important characteristic of FPC, in orderto achieve low transmission loss, it is required that the surface of thecopper foil has high smoothness. Therefore, there is required a methodcapable of bonding a copper foil having a smooth surface and a resinmaterial with high strength.

Patent Document 1 discloses a circuit board (multi-layered wiring board)in which, in a circuit board using a resin cured product as aninsulating layer, in order to obtain high adhesion between a copperwiring layer having a particularly smooth surface and an insulatinglayer, a copper oxide layer present on a surface of the copper wiringlayer is substituted or coated with an oxide and/or a hydroxide of othermetals such as tin, zinc, chromium, cobalt and aluminum to form a layerof an amine-based silane coupling agent having a silanol group or amixture thereof, which is covalently bonded to the oxide and hydroxidelayers, and a vinyl-based silane coupling agent layer having acarbon-carbon unsaturated double bond is further formed thereon to forma covalent bond with a vinyl group contained in a resin cured article ofthe insulating layer.

There is disclosed, as the method for producing a circuit board, amethod including the followings: a copper oxide layer on a coppersurface is substituted or coated with a metal oxide layer and/or ahydroxide layer made of tin, zinc, chromium, cobalt and aluminum byplating, sputtering or vapor deposition; the metal oxide and hydroxidelayers increase the adhesion between the silane coupling agent and themetal layer; the residual silanol group in the amine-based silanecoupling agent layer and the silanol group of the vinyl-based silanecoupling agent layer form a covalent bond; a carbon-carbon unsaturateddouble bond of the vinyl-based silane coupling agent forms a covalentbond with the vinyl compound in the insulating layer; and the resincured article of the insulating layer is cured under pressure and heat.

This circuit board is complicated in configuration and complicated inproduction process.

Patent Document 2 discloses a flexible laminate in which a silanecoupling agent is interposed between a base film of polyethylenenaphthalate (PEN) which is a polyester-based resin and a conductivelayer of copper. The patent document mentions that a hydrolyzablefunctional group of a silane coupling agent reacts with water to form asilanol group and bonds with metal such as copper, and an organicfunctional group is bonded to PEN by the reaction. There is alsodisclosed a lamination step in which a copper alloy is laminated on abase film coated with a silane coupling agent by a sputtering method,followed by subjecting to copper plating to form a conductive layer.

Patent Documents 3 to 6 disclose a material of copper or aluminum whosesurface is not roughened, or a surface-treated metallic material inwhich a plated material obtained by subjecting the metallic material tosilver, nickel or chromate plating is surface-treated with a silane ortitanium coupling agent. The patent documents also disclose a method ofproducing a composite in which a liquid crystal polymer (hereinafterreferred to as LCP) film having a polyester structure is pressure-bondedto the surface-treated metallic material or a polymer is bonded byinjection molding. The patent documents mention that a coupling agentfor a surface treatment of metal or a plated material thereof ispreferably a coupling agent having a nitrogen-containing functionalgroup, i.e., an amine-based silane or titanium coupling agent, which iseffective because the coupling agent satisfactorily adheres to metalsand has high peel strength (peeling strength).

Patent Document 7 discloses a surface treatment agent containing a novelamino group- and alkoxysilane group-containing triazine derivativecompound. The patent document discloses that these materials can bebonded to each other by applying a surface treatment agent containingthis novel compound to various metallic materials and polymer materials,followed by hot pressing. The patent document also mentions that, whenthe novel compound is surface-treated and coated with other reagents, areaction between the functional group present in the film of the novelcompound and other reagents occurs, thus being converted to a materialhaving various functions.

PRIOR ART DOCUMENT

Patent Document

-   Patent Document 1: JP 2011-91066 A-   Patent Document 2: JP 2010-131952 A-   Patent Document 3: JP 2014-27042 A-   Patent Document 4: JP 2014-27053 A-   Patent Document 5: JP 2014-25095 A-   Patent Document 6: JP 2014-25099 A-   Patent Document 7: WO 2013/186941 A

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

When a polyester-based resin film, e.g., a liquid crystal polymer (LCP)is used as an insulating material for forming a printed wiring board,there is an advantage that the transmission loss of the high frequencysignal transmission line can be reduced. However, when thepolyester-based resin material and the copper wiring are bonded to eachother with the silane coupling agent disclosed in Patent Documents 1 to6, the reaction of the coupling agent may not proceed as expected due tothe chemical structure of the polyester-based resin. Therefore, an errorin bonding strength between the polyester-based resin material and thecopper wiring may increase (i.e., inferior reproducibility of thebonding strength), leading to a decrease in bonding strength.

Since the novel compound disclosed in Patent Document 7 has an aminogroup and an alkoxysilane group introduced into a triazine ring, when asurface treatment agent containing the compound is used, the chemicalbondability between the metal and resin increases as compared with theexisting silane coupling agent.

However, there is required a method capable of obtaining higher bondingstrength.

Thus, an object of the present disclosure is to provide a copper alloyarticle in which a polyester-based resin body and a copper alloysubstrate are bonded to each other with sufficiently high bondingstrength, and a method for producing thereof.

Means for Solving the Problems

The inventors of the present invention have intensively studied so tosolve the above problems and found solution means with the followingconfigurations, thus completing the present invention.

An aspect 1 of the present invention is directed to a copper alloyarticle including:

a substrate made of a copper alloy;

a polyester-based resin body; and

a compound layer for bonding the substrate and the polyester-based resinbody, wherein

the compound layer contains;

-   -   a compound having a nitrogen-containing functional group and a        silanol group, and    -   an alkane type amine-based silane coupling agent.

An aspect 2 of the present invention is directed to the copper alloyarticle according the aspect 1, wherein the nitrogen-containingfunctional group has a nitrogen-containing 5-membered or higher-memberedcyclic structure.

An aspect 3 of the present invention is directed to the copper alloyarticle according to the aspect 2, wherein the 5-membered orhigher-membered cyclic structure is a triazole or triazine structure.

An aspect 4 of the present invention is directed to the copper alloyarticle according to any one of the aspects 1 to 3, wherein thesubstrate has a surface roughness Ra of 0.1 μm or less.

An aspect 5 of the present invention is directed to the copper alloyarticle according to any one of the aspects 1 to 4, wherein thepolyester-based resin body is made of a polyester-based resin selectedfrom the group consisting of polyethylene terephthalate, polymethyleneterephthalate, polybutylene terephthalate, polyethylene naphthalate,polybutylene naphthalate and a liquid crystal polymer.

An aspect 6 of the present invention is directed to the copper alloyarticle according to any one of the aspects 1 to 5, wherein an oxidelayer and a rust preventive layer are absent on a surface of thesubstrate.

An aspect 7 of the present invention is directed to a polyester-basedresin member including:

a polyester-based resin body; and

a compound layer provided on a surface of the polyester-based resinbody, wherein

the compound layer contains;

-   -   a compound having a nitrogen-containing functional group and a        silanol group, and    -   an alkane type amine-based silane coupling agent.

An aspect 8 of the present invention is directed to the polyester-basedresin member according to the aspect 7, wherein the nitrogen-containingfunctional group has a nitrogen-containing 5-membered or higher-memberedcyclic structure.

An aspect 9 of the present invention is directed to the polyester-basedresin member according to the aspect 8, wherein the 5-membered orhigher-membered cyclic structure is a triazole or triazine structure.

An aspect 10 of the present invention is directed to the polyester-basedresin member according to any one of the aspects 7 to 9, wherein thepolyester-based resin body is made of a polyester-based resin selectedfrom the group consisting of polyethylene terephthalate, polymethyleneterephthalate, polybutylene terephthalate, polyethylene naphthalate,polybutylene naphthalate and a liquid crystal polymer.

An aspect 11 of the present invention is directed to copper alloy memberincluding:

a substrate made of a copper alloy; and

a compound layer provided on a surface of the substrate, wherein

the compound layer contains;

-   -   a compound having a nitrogen-containing functional group and a        silanol group, and    -   an alkane type amine-based silane coupling agent.

An aspect 12 of the present invention is directed to the copper alloymember according to the aspect 11, wherein the nitrogen-containingfunctional group has a nitrogen-containing 5-membered or higher-memberedcyclic structure.

An aspect 13 of the present invention is directed to the copper alloymember according to the aspect 12, wherein the 5-membered orhigher-membered cyclic structure is a triazole or triazine structure.

An aspect 14 of the present invention is directed to a method forproducing a polyester-based resin member including; a polyester-basedresin body, and a compound layer provided on a surface of thepolyester-based resin body, the method including:

bringing a solution into contact with a surface of the polyester-basedresin body, the solution containing; a compound having anitrogen-containing functional group and a silanol group, and an alkanetype amine-based silane coupling agent, and then

heat-treating the polyester-based resin body.

An aspect 15 of the present invention is directed to a method forproducing a copper alloy article including; a substrate made of a copperalloy, a polyester-based resin body, and a compound layer for bondingthe substrate and the polyester-based resin body, the method including:

obtaining a polyester-based resin member by the method according to theaspect 14;

cleaning a surface of the substrate with an aqueous acid solution; and

bonding the substrate and the polyester-based resin body by bonding thecompound layer and the cleaned surface of the substrate.

An aspect 16 of the present invention is directed to a method forproducing a copper alloy member including; a substrate made of a copperalloy, and a compound layer provided on a surface of the substrate, themethod including:

cleaning the substrate with an aqueous acid solution, and

bringing a solution into contact with a surface of the substrate, thesolution containing; a compound having a nitrogen-containing functionalgroup and a silanol group, and an alkane type amine-based silanecoupling agent; and then

heat-treating the substrate.

An aspect 17 of the present invention is directed to a method forproducing a copper alloy article including; a substrate made of a copperalloy, a polyester-based resin body, and a compound layer for bondingthe substrate and the polyester-based resin body, the method including:

obtaining a copper alloy member by the method according to the aspect16; and

bonding the substrate and the polyester-based resin body by bonding thecompound layer and the polyester-based resin body.

An aspect 18 of the present invention is directed to the methodaccording to any one of the aspects 14 to 17, wherein a molarconcentration ratio of the compound having the nitrogen-containingfunctional group and the silanol group to the alkane type amine-basedsilane coupling agent in the solution is 1:0.5 to 1:15.

Effects of the Invention

According to the present invention, it is possible to bond apolyester-based resin body and a copper alloy substrate to each otherwith sufficient bonding strength through a compound layer containing twoor more compounds.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic sectional view of a copper alloy article accordingto Embodiment 1 of the present invention.

FIG. 2 is an XPS spectrum of an LCP film surface coated with ImS.

FIG. 3 is an XPS spectrum of an LCP film surface coated with AAS.

FIG. 4 is an XPS spectrum of an LCP film surface coated with a mixtureImS and AAS.

FIG. 5(a) and FIG. 5(b) are schematic cross-sectional views forexplaining a first method for producing a copper alloy article accordingto Embodiment 1.

FIG. 6(a) and FIG. 6(b) are schematic cross-sectional views forexplaining a second method for producing a copper alloy articleaccording to Embodiment 1.

FIG. 7 is an XPS spectrum of a copper foil piece surface coated withAST.

FIG. 8 is an XPS spectrum of a copper foil piece surface coated withAAS.

FIG. 9 is an XPS spectrum of a copper foil piece surface coated with anaqueous mixed solution of AST and AAS.

FIG. 10 is an XPS spectrum of a copper foil piece surface coated with anaqueous mixed solution of AST and AAS.

FIG. 11 is an XPS spectrum of a copper foil piece surface coated with anaqueous mixed solution of AST and AAS.

FIG. 12 is an XPS spectrum of a copper foil piece surface coated with anaqueous mixed solution of AST and AAS.

FIG. 13 is an FT-IR chart of an LPC test piece made from a copper cladlaminate of Comparative Example 4.

FIG. 14 is an FT-IR chart of an LPC test piece made from a copper cladlaminate of Comparative Example 5.

FIG. 15 is an FT-IR chart of an LPC test piece made from a copper cladlaminate of Example 6.

MODE FOR CARRYING OUT THE INVENTION

The inventors of the present invention have found that when a compoundlayer for bonding a copper alloy substrate and a polyester-based resinbody contains two types of compounds, the bonding strength can beincreased as compared with the case where only one of the compounds iscontained, thus completing the copper alloy article according to thepresent disclosure.

Specifically, as a first compound, a compound having both anitrogen-containing functional group and a silanol group is used. As thesecond compound, an alkane type amine-based silane coupling agent isused. Namely, the present disclosure is directed to a copper alloyarticle in which a copper alloy substrate and a polyester-based resinbody are bonded to each other through a compound layer interposedtherebetween, the compound layer containing a first compound which has anitrogen-containing functional group and a silanol group and a secondcompound which is an alkane type amine-based silane coupling agent.

Embodiments according to the present invention will be described below.

Embodiment 1

FIG. 1 is a schematic sectional view of a copper alloy article 3according to Embodiment 1, which includes a copper alloy substrate 10, apolyester-based resin main body 40 and a compound layer 20 disposedtherebetween. The copper alloy substrate 10 and the polyester-basedresin main body 40 are bonded to each other through the compound layer20 interposed therebetween.

The copper alloy substrate 10 is made of pure copper or various copperalloys, and any copper alloy used industrially can be used as the copperalloy.

For the copper alloy substrate 10, for example, a copper foil such as anelectrolytic copper foil or a rolled copper foil can be applied. Inparticular, a rolled copper foil having high flexibility is suitable forFPC.

The polyester-based resin body 40 is made of a polyester-based resin.The polyester-based resin is, for example, a polycondensate of apolyvalent carboxylic acid (dicarboxylic acid) and a polyalcohol (diol).Polyethylene terephthalate (PET), polymethylene terephthalate,polybutylene terephthalate, polyethylene naphthalate, polybutylenenaphthalate and a liquid crystal polymer (LCP) are suitable.

For the polyester-based resin body 40, for example, a polyester-basedresin film, a polyester-based resin plate or the like can be employed.In particular, an LCP film has low dielectric constant and lowdielectric loss tangent in material properties, so that it has anadvantage that the transmission loss of the high frequency signal lineis reduced particularly when applied to FPC. Furthermore, since the LCPfilm has very low water absorption rate, it exhibits satisfactorydimensional stability even under high humidity.

As an example, detailed description will be made of a copper alloyarticle using a rolled copper foil as the copper alloy substrate 10 andusing an LCP film as the polyester-based resin body. It is also possibleto similarly configure and produce the copper alloy article 3 using thecopper alloy substrate 10 and the polyester-based resin body 40 in otherforms.

(1) Selection of Rolled Copper Foils

In Embodiments 1 and 2, in order to reduce the transmission loss of highfrequency signals on the printed circuit board, the copper alloysubstrate 10 preferably has a flat surface, for example, the surfaceroughness Ra is preferably 0.1 μm or less. In Embodiment 2 mentionedlater, it is preferable that the copper alloy is exposed on the surfaceof the copper alloy substrate 10. Therefore, investigation is made of aselection method of the copper alloy substrate 10 suitable for anyembodiment.

First, three types of commercially available copper foils (copper foilsA to C) are selected for a copper foil having a thickness of 18 μm,which is most demanded by FPC, and measurement of the surface layer isperformed by X-ray photoelectron spectroscopy (XPS)

TABLE 1 Surface roughness Copper Surface layer (μm) foil XPS analysisR_(a) R_(z) Remarks A Zinc plating — 0.75 Used in existing FCCL B Oxide,Rust 0.05 0.4 Slight oil spots preventive C Oxide, Rust 0.15 —Significant oil spots preventive

A copper foil A is used for existing FPC and, when measured by XPS, zincwas detected. Namely, it has been found that the copper foil A isgalvanized. Since a copper foil having no plating layer is preferable asa copper foil suitable for Embodiment 2, the copper foil A was excluded.

Although there was no plating layer on the surface of the copper foils Band C, elements derived from oxidation of copper and the rust preventiveapplied to the copper foil surface (e.g., carbon, etc.) were detected.

With respect to these copper foils B and C, the measurement of thesurface roughness and electron microscope (SEM) analysis of the surfacewere performed.

The surface roughness Ra was measured by a laser microscope. The copperfoil B had Ra of 0.05 μm and the copper foil C had Ra of 0.15 μm.

As a result of confirming wrinkle-like dents (oil spots) on the surfaceby SEM observation, slight oil spots were observed in the copper foil Bas compared with the copper foil C.

From these results, it was judged that the copper foil B had highersurface smoothness, and the copper foil B was used as the copper alloysubstrate 10.

(2) Cleaning of Copper Foil (Copper Alloy Substrate 10)

A commercially available copper foil is coated with a rust preventive.On a surface of the copper foil, an oxide layer can be formed withpassage of time. In the case of a copper alloy article such as FPC, inorder to exhibit properties of the copper foil, for example, electricconductivity to the utmost, it is desired that the rust preventive andthe oxide layer are removed from the surface of the copper foil toexpose copper on the surface of the copper foil. In order to do that,there is a need to perform cleaning (acid cleaning) to remove the rustpreventive and the oxide layer before using the copper foil. Therefore,using the copper foil B as a sample, the conditions of acid cleaningwere investigated.

As a cleaning solution, 15% sulfuric acid and 1% hydrochloric acid wereused at room temperature. The sample was immersed in a cleaning solutionfor 0 minute (without cleaning), 1 minute and 5 minutes, taken out fromthe cleaning solution, sufficiently washed with ion exchanged water, andthen dried. Thereafter, the surface of the sample was analyzed by XPS todetermine the cleaning level.

The cleaning level of the copper foil surface after acid washing wasjudged whether or not the rust preventive remains on the surface.Specifically, the copper foil surface after cleaning was measured by XPSand qualitatively judged according to the presence or absence of a peakof nitrogen (N) (peak of nitrogen N1s orbit at binding energy of around400 eV) derived from the rust preventive. The case where a peakattributed to nitrogen (N) could be confirmed in the XPS spectrum wasjudged to be “present”, whereas, the case where a peak could not beconfirmed was judged to be “none”. The measurement results are shown inTable 2.

The oxide layer can also be used as evaluation criteria for the cleaninglevel. However, even if the oxide layer can be completely removed fromthe surface of the copper foil by acid cleaning, copper on the copperfoil surface reacts with oxygen in the atmosphere to form a trace amountof an oxide at the moment when the copper foil is taken out from thecleaning solution. In surface analysis by XPS, the trace amount of theoxide is also detected, so that it is difficult to accurately judge thecleaning level.

TABLE 2 Immersion time Cleaning solution 0 minute 1 minutes 5 minutes15% Sulfuric acid Present None None 1% Hydrochloric acid Present NoneNone

As shown in Table 2, in the case of any cleaning solution (aqueous acidsolution), the peak derived from the nitrogen N1s orbital disappearedfrom the copper foil surface within the immersion time of 1 minute,leading to a minor peak of the Cu2p orbital derived from the oxide.Therefore, it was judged that the rust preventive and the oxide adheredto the copper foil can be removed by immersing in the cleaning solutionfor 1 minute. In the following embodiments, a copper foil cleaned with1% hydrochloric acid for 1 minute, which is easy to handle, is used.

Even in the copper alloy article using the copper foil, it can be seenthat a copper foil cleaned with an acid was used by XPS analysis of thesurface of the copper foil peeled off from the copper alloy article,thereby confirming the peak derived from the N1s orbital and the peakderived from the Cu 2p orbital. It is possible to confirm that no rustpreventive is present since the peak derived from the N is orbit is notdetected. It is possible to confirm that no oxide layer is present dueto minor peak derived from the Cu 2p orbital (e.g., a peak intensity of1/10 or less of the peak intensity of a peak derived from Cu—O presentat around 935 eV, particularly a peak intensity of 1/20 or less). Asmentioned above, even if the copper foil is cleaned with an acid toremove the oxide layer, a small amount of the oxide is formed byextracting into the atmosphere thereafter. However, since such a traceamount of the oxide does not substantially affect properties of thecopper foil (in particular, the bonding force with the polyester-basedresin body), it is considered that there is substantially no oxidelayer.

(3) Compound Layer

The compound layer 20 contains two types of compounds, a first compoundhaving a nitrogen-containing functional group and a silanol group, and asecond compound which is an alkane type amine-based silane couplingagent. Both compounds can be used alone as a silane coupling agent. Inthe present disclosure, it has been found that the bonding strength canbe increased as compared with the case where these compounds are usedalone by using a bulky first compound and a linear second compound incombination.

The nitrogen-containing functional group is effective for increasing thebonding strength to the copper alloy substrate 10 because of its highchemical adsorptivity to copper. The silanol group is effective forincreasing the bonding strength to the polyester-based resin body 40because of its high chemical adsorptivity to the ester structure of thepolyester-based resin. Therefore, the compound having anitrogen-containing functional group and a silanol group (firstcompound) is suitable for bonding the copper alloy substrate 10 and thepolyester-based resin body 40 to each other.

The inventors of the present invention have found for the first timethat, when a linear silane coupling agent (second compound) is allowedto coexist with the first compound mentioned above, it is possible toincrease the bonding strength between the copper alloy substrate 10 andthe polyester-based resin body 40. The reason why such effect isobtained is not clear, but is considered to be due to the followingmechanism.

The second compound, which is an alkane type amine-based silane couplingagent, has comparatively low bulky structure (e.g., a linear structure).In general, the first compound having a nitrogen-containing functionalgroup and a silanol group has a bulky structure as compared with thelinear second compound. Therefore, in a situation where only the firstcompound is present, it is difficult for first compounds to come closeto each other. Since the second compound can penetrate into the spacebetween the bulky first compounds, the density of the compound in thecompound layer 20 can be increased. Thereby, when the polyester-basedresin body 40 and the copper alloy substrate 10 are bonded to each otherthrough the compound layer 20 interposed therebetween, the bondingstrength can be increased.

Therefore, when bonding is performed using the first compound whichcoexists with the second compound, it is possible to improve the bondingstrength between the copper alloy substrate 10 and the polyester-basedresin body 40 as compared with the case where bonding is performed usingthe first compound or the second compound alone.

In this way, by using two types of compounds having different structuresin combination, it is possible to roughen each surface of the copperalloy substrate 10 and the polyester-based resin body 40, or to firmlybond the copper alloy substrate 10 and the polyester-based resin body 40to each other without forming a metal oxide layer on the surface of thecopper alloy substrate.

The “nitrogen-containing functional group” possessed by the firstcompound preferably has a nitrogen-containing 5-membered orhigher-membered cyclic structure. The nitrogen-containing 5-membered orhigher-membered cyclic structure can be, for example, a triazole ortriazine structure.

Since the structure of the first compound becomes particularly bulky inthe case of having the 5-membered or higher-membered cyclic structure,it becomes difficult for the first compounds to come closer to eachother, thus exerting more remarkable effect of improving the bondingstrength due to mixing of the second compound.

It is possible to confirm by a method of analysis such as XPS analysisthat the compound layer contains a first compound and a second compound.For example, in the spectrum obtained by the XPS analysis of thecompound layer, a peak attributed to the nitrogen atom bonded by adouble bond, a peak attributed to the nitrogen atom of a primary aminogroup, a peak attributed to the nitrogen atom of a secondary amino groupand the like are included within a range of the binding energy at whichan N1s peak appears. These peaks can be identified by an analysisspectrum of an XPS spectrum.

When the nitrogen atom contained in the first compound and the nitrogenatom contained in the second compound are in different bonding states,and thus the peaks of the XPS spectrum attributed to those nitrogenatoms are identifiable. Thus, it is possible to specify that the firstcompound and the second compound are contained in the compound layer.

Selection of Compound

Hereinafter, the bonding strength between various compounds and thecopper alloy substrate was compared.

Five types of compounds shown in Table 3 (hereinafter, each compound isreferred to as the symbol mentioned in Table 3) were selected. Regardingthe compound whose chemical name is disclosed, the chemical name wasdescribed. Meanwhile, regarding the compound ImS which is not disclosedin detail, the disclosed basic structure was described. Main functionalgroups possessed by these compounds are shown in Table 4. It is knownthat an alkoxysilane group converted into a silanol group in an aqueoussolution. Among them, only the compound ET has no alkoxysilane group andis not a silane coupling agent.

TABLE 3 Manufacturer Symbol Compound Product name ET1,3,5-Tris-(2,3-epoxypentyl)-1,3,5- Nissan Chemicaltriazine-2,4,6(1H,3H,5H)trione Industries, Ltd. TEPIC-VL AST2-(3-Triethoxysilylpropyl)amino- Sulfur Chemical4,6-di(2-aminoethyl)amino-1,3,5- Laboratory Inc. triazine ImSImidazole-based silane compound JX Nippon Mining & Metals CorporationIS-1000 AAS N-2(aminoethyl)-3- Shin-Etsu Chemicalaminopropyltrimethoxysilane Co., Ltd. KBM-603 AS 3-Aminopropyltrimethoxysilane Shin-Etsu Chemical Co., Ltd. KBM-903

TABLE 4 Symbol Compound Main functional group ET1,3,5-Tris-(2,3-epoxypentyl)- Basic structure: 6-Membered1,3,5-triazine- triazine ring 2,4,6(1H,3H,5H)trione Epoxy group Oxogroup AST 2-(3- Basic structure: 6-MemberedTriethoxysilylpropyl)amino-4,6- triazine ringdi(2-aminoethyl)amino-1,3,5- Alkoxysilane group triazine Amino group ImSImidazole-based silane Basic structure: 5-Membered compound imidazolering Alkoxysilane group AAS N-2(aminoethyl)-3- Basic structure: Alkaneaminopropyltrimethoxysilane Alkoxysilane group Amino group AS3-Aminopropyltrimethoxy silane Basic structure: Alkane Alkoxysilanegroup Amino group

A copper foil, an LCP film (Vecstar CT-Z, manufactured by Kuraray Co.,Ltd.) and a PET film (UF, manufactured by Teijin DuPont Films), whichwere cleaned with 1% hydrochloric acid for 1 minute and thensufficiently washed with ion exchanged water, were coated with fivetypes of aqueous bonding compound solutions each having a concentrationof 0.1% using a dip coater manufactured by J.P.C Co., Ltd., followed bydrying and further heat treatment at 100° C. for 5 minutes. The coatedsurface was analyzed by XPS analysis. The analysis results aresummarized in Table 7. Regarding the PET film, only ET coating and ASTcoating were performed.

TABLE 5 XPS analysis results Symbols Copper foil LCP film PET film ETCu2p orbital peak: only C1s orbital peak: no C1s orbital peak: no Cu(0-valent) peak exists chemical shift exists in chemical shift exists inat around 930-935 eV, C—O/C═O peaks at C—O/C═O peaks at and no Cu—N peakexists. 286-288 eV. 286-288 eV. Physical adsorption AST Cu2p orbitalpeak: Cu—N C1s orbital peak: C1s orbital peak: bond peak exists atchemical shift exists in chemical shift exists in around 936 eV, and noC—O/C═O peaks at C—O/C═O peaks at Cu (0-valent) peak exists. 286-288 eV286-288 eV ImS Cu2p orbital peak: Cu C1s orbital peak: (0-valent)exists, and chemical shift exists in Cu—N bond peak C—O/C═O peaks atexists at 286-288 eV. Unreacted around 936 eV. ester group exists at 289eV. AAS Cu2p orbital peak: Cu C1s orbital peak: (0-valent) exists, andchemical shift exists in Cu—N bond peak C—O/C═O peaks at exists at286-288 eV. Unreacted around 936 eV. ester group exists at 289 eV. ASCu2p orbital peak: Cu C1s orbital peak: (0-valent) peak is high, andchemical shift exists in Cu—N bond peak C—O/C═O peaks at exists at286-288 eV. Unreacted around 936 eV. ester group exists at 289 eV.

Compound ET

A compound ET is a compound having a nitrogen-containing functionalgroup and a silanol group (i.e., first compound), and the compound EThas three epoxy groups and three oxo groups (C═O) in a 6-memberedtriazine ring containing three nitrogen atoms (N). In the copper foilcoated with ET, a peak showing chemical adsorption between copper (Cu)and the N atom did not appear. In LCP and PET coated with ET, there isno chemical shift of the peak showing chemical adsorption with the epoxygroup. These results revealed that ET does not chemically adsorbed toeach surface of a copper foil, LCP and PET, and is only physicallyadsorbed.

Compound AST

A compound AST is a compound having a nitrogen-containing functionalgroup and a silanol group (i.e., first compound), and the compound ASThas one alkoxysilane group and two amino groups in a 6-membered triazinering containing three nitrogen atoms. In the copper foil coated withAST, when observing the Cu 2p orbital peak of copper, a peak showingbonding between Cu and N was confirmed. In LCP and PET coated with AST,peaks showing C—O/C═O bonds appeared at 286 to 288 eV of the C1s orbitalpeak, and both peaks shifted from the peak position of the originalfilm. These results revealed that, regarding AST, N of the 6-memberedtriazine ring and N od the amino group are chemically adsorbed to copperand the silanol group is chemically adsorbed to the ester structure ofLCP and PET.

Compound ImS

A compound ImS is a compound having a nitrogen-containing functionalgroup and a silanol group (i.e., first compound), and has a structure inwhich a 5-membered imidazole ring and one alkoxysilane group areconnected to each other. In the copper foil coated with ImS, whenobserving the Cu 2p orbital peak of copper, there was a peak showingbonding between Cu and N, which shows that the imidazole group ischemically adsorbed to copper. At the same time, there was also a peakof Cu (0-valent), which shows that there is a part where no ImS ispresent on the surface of copper. In AST, the peak of Cu (0-valent) wasnot observed, which showed that AST is chemically adsorbed to the coppersurface at higher density than that of ImS.

Meanwhile, in LCP coated with ImS, the peak showing bonding of C—O andC═O at 286 to 288 eV shifted from the peak position of the originalfilm, which showed that chemical adsorption occurs. There was also apeak of the unreacted ester group at 289 eV, which showed that there wasa portion where ImS is not chemically adsorbed to the LCP. In AST, sincethe peak of such unreacted ester group was not observed, it is judgedthat AST is higher in chemical adsorptivity to the ester structure ofLCP than that of ImS.

Compounds AAS and AS

Compounds AAS and AS are alkane type amine-based silane coupling agents(i.e., second compound), and are typical compounds which are widelyapplied for bonding between copper and resins in the prior art document.In the copper foil coated with these compounds, when observing the Cu 2porbital peak of copper, there is a Cu (0-valent) peak like ImS, whichshowed that there is the portion where AAS or AS is not adsorbed on thesurface of copper. Heretofore, a number of documents have addressed thatthe silanol group is chemically adsorbed to the copper surface. However,it became clear that, unlike the documents, the chemical adsorptivity ofthese compounds deteriorate on the copper surface cleaned sufficientlywith an acid

As mentioned previously, when the copper surface is cleaned with an aciduntil the antioxidant applied thereon is completely removed, the oxideof copper formed on the surface by being exposed to the naturalenvironment is also removed, leading to drastic decrease in amountthereof. With regard to the silanol group chemically adsorbed to theoxide, adsorption sites have been markedly reduced on the surface ofcopper cleaned sufficiently with an acid. Meanwhile, since the Cu—N bondpeak is observed, the amino group is chemically adsorbed on the copperfoil surface. At the same time, the peak of Cu (0-valent) attributed tothe copper surface, on which no compound is adsorbed, also appeared,which showed that the amino group of an alkane has low chemicalabsorptivity.

In LCP coated with AAS and AS, there is a peak of the unreacted estergroup at 289 eV, and it is judged that the chemical adsorptivity to LCPis also low.

The substituent of the nitrogen-containing cyclic compound may be, inaddition to the amino group of AST, a ureido group, an isocyanate groupor the like.

Specification of Compound contained in Compound Layer

A relationship between each compound and the XPS spectrum was examinedusing ImS as the first compound and using AAS as the second compound.

An aqueous solution containing a predetermined compound was applied toan LCP film and then heat-treated at 100° C. for 5 minutes. The film ofthe compound formed on the surface of the LCP film was subjected to XPSanalysis.

FIG. 2 shows an N1s peak of an XPS spectrum of the ImS film, and thespectrum is separated into two spectra by analysis software of the XPSspectrum.

The first peak appearing at the position of the binding energy of 400.87eV is attributed to a nitrogen atom bonded by a double bond contained inthe 5-member imidazole ring (labeled with “—C═N—C” in FIG. 2).

The second peak appearing at the position of the binding energy of398.99 eV is attributed to an amino type nitrogen atom (labeled “>N-” inFIG. 2) contained in the 5-membered imidazole ring.

The intensity of the second peak is almost the same as that of the firstpeak.

FIG. 3 shows an N1s peak of an XPS spectrum of the AAS film, and thespectrum is separated into three spectra by analysis software.

The peak appearing at the position of the binding energy of 399.98 eV isattributed to a nitrogen atom of a primary amino group (labeled with“—NH₂” in FIG. 3).

The peak appearing at the position of the binding energy of 399.12 eV isattributed to a nitrogen atom of a secondary amino group (labeled with“—NH” in FIG. 3).

FIG. 4 shows an N1s peak of an XPS spectrum of the film containing ImSand AAS, and the spectrum is separated into two spectra by analysissoftware.

The first peak appearing at the position of the binding energy of 400.97eV is attributed to a nitrogen atom bonded by a double bond contained inthe 5-member imidazole ring (labeled with “—C═N—C” in FIG. 4). Sincethis peak is present, it can be seen that ImS is contained in the filmof the measured compound.

Regarding the second peak appearing at the position of the bindingenergy of 399.44 eV, a peak attributed to an amino type nitrogen atom(labeled with “>N-” in FIG. 4), a peak attributed to a nitrogen atom ofa primary amino group (labeled with “—NH₂”) and a peak attributed to anitrogen atom of a secondary amino group (labeled with “—NH”) which areoverlapped with each other. The intensity of the second peak is about2.5 times the intensity of the first peak. As compared with the XPSspectrum of ImS shown in FIG. 2, since the intensity of the second peakto that of the first peak remarkably increases, it can be seen that acompound having an amino group (AAS in this example) is contained, inaddition to ImS.

XPS analysis of the film of the compound containing the first compound,ImS, revealed that the peak (about 400.8 to about 401.0 eV) attributedto a nitrogen atom bonded by the double bond (—C═N—C—) is confirmed.Since this peak is separated from the peak attributed to a nitrogen atomof an amino group contained in the second compound (about 398.5 to about400.0 eV), it can be confirmed that the first compound and the secondcompound are contained.

A method for producing a copper alloy article 3 according to the presentembodiment will be described below with reference to FIGS. 5(a) and5(b).

<1-1. Formation of Compound Layer 20>

A solution containing a first compound having a nitrogen-containingfunctional group and a silanol group and a second compound which is analkane type amine-based silane coupling agent is brought into contactwith a surface of a polyester-based resin body 40. The solution can bebrought into contact with the surface of the polyester-based resin body40 by a known method such as a coating or spraying method. Thereafter, aheat treatment is performed, thus making it possible to form a compoundlayer 20 on the surface of the polyester-based resin body (FIG. 5(a)).Thereby, a polyester-based resin member 47 including the polyester-basedresin body 40 and the compound layer 20 is obtained.

A first solution containing the first compound and a second solutioncontaining the second compound may be separately prepared instead of thesolution containing the first compound and the second compound. Bysequentially bringing the first solution and the second solution intocontact with the surface of the polyester-based resin body 40, the firstcompound and the second compound can be mixed and adsorbed on thesurface of the polyester-based resin body 40. The second solution may becontacted after contacting the first solution, or the second solutionmay be contacted after contacting the first solution.

In a compound having a nitrogen-containing functional group and asilanol group, it is preferable that the nitrogen-containing functionalgroup has a nitrogen-containing 5-membered ring or higher-memberedcyclic structure. It is particular preferable that the 5-membered ringor higher-membered cyclic structure is a triazole or triazine structure.Examples of specific compounds include AST analogous compounds in whicha part of functional groups of AST, ImS and AST mentioned in Table 5 aresubstituted with other functional groups, imidazole silane couplingagents and the like. Examples of the AST analogous compound includecompounds in which a triethoxy group of AST is substituted with atrimethoxy group, and compounds in which an amino substituent of a4,6-di(2-aminoethyl)amino group of AST is substituted with anN-2-(aminoethyl)-3-aminopropyl group, a 3-aminopropyl group, anN-(1,3-dimethyl-methylidyne)propylamino group, an N-phenyl-3-aminopropylgroup, an N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group or a3-ureidopropyl group. Examples of the imidazole silane coupling agentinclude tris-(trimethoxysilylpropyl)isocyanurate, and those having anyone of a 1-imidazolyl group, a 3-imidazolyl group and a 4-imidazolylgroup, together with a trialkoxysilyl group such as a trimethoxy groupor a triethoxy group.

The alkane type amine-based silane coupling agent is preferably a linearalkane type amine-based silane coupling agent. Specific examples of thecompound include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane,N-2-(aminoethyl)-3-aminopropyltrimethoxysilane,3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and thelike.

<1-2. Cleaning of Copper Alloy Substrate 10>

The surface of the copper alloy substrate 10 is cleaned with an aqueousacid solution. Thereby, the oxide layer and the rust preventive presenton the surface of the copper alloy substrate 10 can be removed.

It is possible to employ, as the aqueous acid solution, for example, anaqueous solution of an acid solution, such as sulfuric acid,hydrochloric acid, a mixed solution of sulfuric acid and chromic acid, amixed solution of sulfuric acid and hydrochloric acid, or a mixedsolution of sulfuric acid and nitric acid. Particularly, an aqueoussulfuric acid solution or an aqueous hydrochloric acid solution ispreferable.

Cleaning can be performed by immersing the copper alloy substrate 10 inthe aqueous acid solution for a predetermined time. The immersing timemay be in any range as long as the oxide layer on the surface and therust preventive can be removed and the copper alloy substrate 10 is notsignificantly eroded. For example, when 1% hydrochloric acid is used,the copper alloy substrate can be immersed for 30 seconds to 10 minutes(e.g., 1 minute). When 15% sulfuric acid is used, the copper alloysubstrate may be immersed for 1 to 20 minutes (e.g., 5 minutes).

<1-3. Bonding of Copper Alloy Substrate 10 and Polyester-Based ResinMember 47>

As shown in FIG. 5 (b), by pressing a compound layer 20 of apolyester-based resin member 47 and a cleaned copper alloy substrate 10while they are brought into contact with each other, the polyester-basedresin member 47 and the copper alloy substrate 10 are bonded to eachother, thus making it possible to obtain a copper alloy article 3 asshown in FIG. 1. This can also be regarded as bonding thepolyester-based resin body 40 of the polyester-based resin member 47 andthe copper alloy substrate 10 to each other through the compound layer20 interposed therebetween.

It is preferable to heat the copper alloy substrate 10 and thepolyester-based resin member 47 before or during pressurization sinceheating facilitates bonding. The heating temperature is set at thetemperature at which the polyester-based resin body 40 of thepolyester-based resin member 47 is not melted. Pressurization can beperformed by setting at a surface pressure of 1 MPa to 8 MPa, e.g., 4MPa.

As a modification of the production method, the compound layer 20 may beformed on the surface of the copper alloy substrate 10. Modificationswill be described with reference to FIGS. 6(a) and 6(b).

<2-1. Formation of Compound Layer 20>

A solution containing a compound having a nitrogen-containing functionalgroup and a silanol group is brought into contact with the surface ofthe cleaned copper alloy substrate 10. Thereafter, a heat treatment isperformed, thus making it possible to form a compound layer 20 on thesurface of the copper alloy substrate 10 (FIG. 6(a)). Thereby, a copperalloy member 15 including the copper alloy substrate 10 and the compoundlayer 20 is obtained.

Details of the compound layer 20 are as the same as in the step 1-1.

<2-2. Cleaning of Copper Alloy Substrate 10>

According to the same step as the step 1-2 of Embodiment 1, the surfaceof the copper alloy substrate 10 is cleaned with an aqueous acidsolution to remove the oxide layer and the rust preventive present onthe surface of the copper alloy substrate 10.

<2-3. Bonding of Copper Alloy Member 15 and Polyester-Based Resin Body40>

As shown in FIG. 6(b), by pressing a polyester-based resin body 40 and acompound layer 20 of a copper alloy member 15 while they are broughtinto contact with each other, the polyester-based resin member 40 andthe copper alloy substrate 15 are bonded to each other, thus making itpossible to obtain a copper alloy article 3 as shown in FIG. 1.

The details of pressure bonding are the same as in Embodiment 1.

By preparing the polyester-based resin member 47 including the compoundlayer 20 (FIG. 5(a)) and the copper alloy member 15 including thecompound layer 20 (FIG. 6(a)) and pressing these compound layers 20while they are brought into contact with each other, a copper alloyarticle 3 as shown in FIG. 1 can also be obtained.

The compound layer of the polyester-based resin member 47 may be formedof a first solution containing a first compound having anitrogen-containing functional group and a silanol group, and a compoundlayer of the copper alloy member 15 may be formed of a second solutioncontaining a second compound which is an alkane type amine-based silanecoupling agent. When the compound layer of the polyester-based resinmember 47 and the compound layer of the copper alloy member 15 arebrought into contact with each other during bonding, in case the firstcompound contained in one compound layer and the second compoundcontained in the other compound layer are chemically adsorbed together,the compound layer 20 containing the first compound and the secondcompound can be formed.

When the first compound contained in one compound layer and the secondcompound contained in the other compound layer are not sufficientlychemically adsorbed, the effect of improving the bonding strength maynot be sufficiently exhibited. Therefore, it is preferable toappropriately select the method for formation of a compound layerdepending on the compound to be used.

The invention according to the present disclosure will be described byway of Examples.

Properties of Each Compound

A 50 μm-thick LCP film CT-Z (manufactured by Kuraray Co., Ltd.) was cutinto square with each side of 150 mm to prepare four test pieces (LCPfilm pieces). Each of four types of aqueous compound solutions (aqueousET solution, aqueous AAS solution, aqueous ImS solution, and aqueous ASTsolution) was applied on both surfaces of the test piece of the LCP filmusing a dip coater manufactured by JSP Co., Ltd. The concentration ofeach aqueous solution was adjusted to 0.1%.

A copper foil B (manufactured by UACJ Foil Corporation, thickness: 18μm) was cleaned with 1% hydrochloric acid for 1 minute, sufficientlywashed with ion exchanged water, and then dried. The copper foil B wascut into square with each side of 150 mm to prepare eight test pieces(copper foil pieces). Each of four types of the above aqueous compoundsolutions was applied on both surfaces of the test piece of the copperfoil using a dip coater manufactured by JSP Co., Ltd. One type of anaqueous compound solution was applied to two copper foil pieces.

Thereafter, the LCP film piece and the copper foil piece coated with theaqueous solution were heat-treated at 100° C. for 5 minutes. Thereby, acompound layer was formed on both surfaces of the LCP film piece andboth surfaces of the copper foil piece.

The copper foil piece was placed on both surfaces of the LCP film pieceon which the compound layer was formed, and then the temperature wasraised to 270° C. while pressurizing under a surface pressure of 4 MPausing a vacuum press machine manufactured by Kitagawa Seiki Co., Ltd.,followed by holding for 20 minutes and further heating at 290° C. for 10minutes to prepare a double-sided copper clad laminate. In thisdouble-sided copper clad laminate, a compound layer is placed betweenthe LCP film and the copper foil.

In this test, the aqueous compound solution was applied to both the LCPfilm and the copper foil. Even if the aqueous compound solution wasapplied to any one of them, a compound layer can be formed between theLCP film and the copper foil. That is, the surface to be coated can beappropriately determined depending on the wettability of the compoundsolution, the ease of formation of the compound layer, the requiredamount of the compound and the like.

As a comparative control, a double-sided copper clad laminate wasprepared in the same manner using a test piece in which an aqueouscompound solution is not applied to both the LCP film and the copperfoil.

A test piece was cut out from the double-sided copper clad laminate in astrip shape and the entire surface of the copper foil on the backsurface was removed by etching in accordance with JIS C 6471 8.1“Peeling Strength of Copper Foil”, and then a pattern with a width of 10mm was left by etching to prepare a peeling test piece. The LCP filmside of the back surface of the peeling test piece was fixed to areinforcing plate using a double-sided tape and the copper foil waspeeled in the 180° direction at a peeling rate of 50 mm/min usingAutograph AGS-5kNX manufactured by Shimadzu Corporation, followed by themeasurement of the peeling strength under each condition using threetest pieces. From the peeling test chart, the minimum value and themaximum value were read. The results are shown in Table 6.

TABLE 6 Peeling strength (kN/m) Compound (minimum value/maximum value)Peeling state None 0.16/0.20 Interfacial peeling ET 0.08/0.11Interfacial peeling AAS 0.32/0.37 Scaly cohesive peeling ImS 0.39/0.44Cohesive peeling AST 0.59/0.68 Cohesive peeling

When the compound layer is not provided, the LCP film and the copperfoil were not bonded to each other and peeling occurred at the interfacebetween the copper foil and the LCP film. The minimum value and maximumvalue of the peeling strength were 0.16 kN/m and 0.20 kN/m,respectively.

In case the LCP film and the copper foil were bonded to each otherthrough the compound layer containing the compound ET, peeling occurredat the interface between the copper foil and the LCP film when a peelingtest was performed. The minimum value and the maximum value of thepeeling strength were 0.08 kN/m and 0.11 kN/m, respectively. That is, itcan be said that the copper foil and the LCP film cannot be bonded toeach other using the compound layer containing the compound ET. As shownby the above XPS analysis, it is considered that the compound ET is notchemically adsorbed to both the copper foil and the LCP film, thusfailing to bond them. The results revealed that, even when having a6-membered triazine ring structure, the LCP film and the copper foilcannot be bonded to each other with sufficient strength in case allsubstituents of the nitrogen atom (N) are epoxy groups, that is, thereis no alkoxysilane group.

When the LCP film and the copper foil were bonded to each other throughthe compound layer containing the compound AAS, the thin white LCP filmremained (scaly cohesive peeling) as a result of observation of thepeeling interface of the copper foil after the peeling test. The minimumvalue and the maximum value of the peeling strength were 0.32 kN/m and0.37 kN/m, respectively. As shown by the above XPS analysis, it isconsidered that the compound AAS has low chemical adsorptivity to boththe copper foil and the LCP film, leading to comparatively low peelingstrength.

When the LCP film and the copper foil were bonded to each other throughthe compound layer containing the compound ImS, the white LCP filmremained (cohesive peeling) as a result of observation of the peelinginterface of the copper foil after the peeling test. The minimum valueand the maximum value of the peeling strength were 0.39 kN/m and 0.44kN/m, respectively.

When the LCP film and the copper foil were bonded through the compoundlayer containing the compound AST, the white LCP film remained (cohesivepeeling) as a result of observation of the peeling interface of thecopper foil after the peeling test. The minimum value and the maximumvalue of the peeling strength were 0.59 kN/m and 0.68 kN/m,respectively.

The results revealed that a nitrogen-containing cyclic molecularstructure (compounds ImS and AST) is effective for bonding the coppermetal substrate as compared with an amino group on the linear saturatedcarbon of the alkane type amine-based silane coupling agent (compoundAAS).

Example 1

Examination was made of the effect of compositely adding a compoundhaving a nitrogen atom-containing cyclic molecular structure (firstcompound) and an alkane type amine-based silane coupling agent (secondcompound).

A 50 μm-thick LCP film CT-Z (manufactured by Kuraray Co., Ltd.) was cutinto square with each side of 150 mm to prepare four test pieces (LCPfilm pieces). Four LCP film pieces were prepared. Any one of aqueouscompound solutions containing the compound in Table 7 was coated on bothsurfaces of the LCP film piece using a dip coater manufactured by JSPCo., Ltd. Specifically, in Example 1, a compound layer was formed usingan aqueous mixed solution containing 0.1% by weight of ImS and 1% byweight of AAS. In Comparative Example 2, an aqueous solution containing0.1% by weight of ImS was used. In Comparative Example 1, an aqueoussolution containing 0.1% by weight of AAS was used.

“Copper foil B” (manufactured by UACJ Foil Corporation, thickness: 18μm) shown in Table 1 was cleaned with 1% hydrochloric acid for 1 minute,sufficiently washed with ion exchanged water, and then dried. The copperfoil B was cut into square with each side of 150 mm to prepare testpieces (copper foil pieces). Eight copper foil pieces were prepared.Each of four types of the above aqueous compound solutions was appliedon both surfaces of the copper foil piece using a dip coatermanufactured by JSP Co., Ltd. One type of an aqueous compound solutionwas applied to two copper foil pieces.

Thereafter, the LCP film piece and the copper foil piece coated with theaqueous solution were heat-treated at 100° C. for 5 minutes. Thereby, acompound layer was formed on both surfaces of the LCP film piece andboth surfaces of the copper foil piece.

The copper foil piece was placed on both surfaces of the LCP film pieceon which the compound layer was formed, and then the temperature wasraised to 270° C. while pressurizing under a surface pressure of 4 MPausing a vacuum press machine manufactured by Kitagawa Seiki Co., Ltd.,followed by holding at 270° C. for 20 minutes and further holding at290° C. for 10 minutes to prepare a double-sided copper clad laminate.In this double-sided copper clad laminate, a compound layer is placedbetween the LCP film and the copper foil.

The results of the peeling test are shown in Table 7.

TABLE 7 Peeling strength (kN/m) (minimum value/ Compound maximum value)Peeling state Example 1 ImS + AAS 0.44/0.68 Cohesive peeling ComparativeImS 0.39/0.44 Cohesive peeling Example 1 Comparative AAS 0.32/0.37 Scalycohesive Example 2 peeling

Like Comparative Example 1, when the LCP film and the copper foil arebonded to each other through a compound layer containing only thecompound ImS (first compound), the minimum value and the maximum valueof the peeling strength were 0.39 kN/m and 0.44 kN/m, respectively.

Like Comparative Example 2, when the LCP film and the copper foil werebonded through a compound layer containing only the compound AAS (secondcompound), the minimum value and the maximum value of the peelingstrength were 0.32 kN/m and 0.37 kN/m, respectively.

Meanwhile, like Example 1, when the LCP film and the copper foil arebonded through a compound layer containing both the compound ImS (firstcompound) and the compound AAS (second compound), the minimum value andthe maximum value of the peeling strength were 0.44 kN/m and 0.68 kN/m,respectively.

When compared with the maximum value of the peeling strength, thepeeling strength of Example 1 was about 1.55 times (0.68/0.44) thepeeling strength of Comparative Example 1 and about 1.84 times(0.68/0.37) the peeling strength of Comparative Example 2. That is, ithas been found that it is possible to realize an improvement in peelingstrength by 1.5 times or more as compared with the case of using eachcompound alone only by mixing the compound ImS with the compound AAS,like Example 1. By comparing the maximum value, it is possible to knowhow much the maximum value of the bonding strength, which can berealized by the compound layer as in Example 1, can be improved.

Example 2

In Example 2, a test piece (“double-sided copper clad laminate” in whichan LCP film piece and a copper foil piece are laminated) was formed inthe same manner as in Example 1 using an aqueous compound solutioncontaining the compound in Table 8, and a peeling test was performed.Specifically, in Example 2, a compound layer was formed using an aqueousmixed solution containing 0.1% by weight of AST and 1% by weight of AAS.In Comparative Example 3, an aqueous solution containing 0.1% by weightof AST was used.

The results of the peeling test are shown in Table 8.

TABLE 8 Peeling strength (kN/m) (minimum value/ Compound maximum value)Peeling state Example 2 AST + AAS 0.68/0.77 Cohesive peeling ComparativeAAS 0.32/0.37 Scaly cohesive Example 2 peeling Comparative AST 0.59/0.68Cohesive peeling Example 3

As mentioned above, in Comparative Example 2, when the LCP film and thecopper foil are bonded to each other through the compound layercontaining only the compound AAS (second compound), the minimum valueand the maximum value of the peeling strength were 0.32 kN/m and 0.37kN/m, respectively.

Like Comparative Example 3, when the LCP film and the copper foil arebonded to each other through a compound layer containing only thecompound AST (first compound), the minimum value and the maximum valueof the peeling strength were 0.59 kN/m 0.68 kN/m, respectively.

Meanwhile, like Comparative Example 2, when the LCP film and the copperfoil are bonded to each other through a compound layer containing boththe compound AST (first compound) and the compound AAS (secondcompound), the minimum value and the maximum value of the peelingstrength were 0.68 kN/m and 0.77 kN/m, respectively.

When compared with the maximum value of the peel strength, the peelingstrength of Example 2 was about 2.08 times (0.77/0.37) the peelingstrength of Comparative Example 2 and about 1.13 times (0.77/0.68) thepeeling strength of Comparative Example 3. That is, it has been foundthat it is possible to realize an improvement in peeling strength of1.13 times or more as compared with the case of using each compoundalone only by mixing the compound AST with the compound AAS, likeExample 2. Although the bonding strength achieved by using AST alone issufficiently high among conventional silane coupling agents, it ispossible to further improve the bonding strength according to theembodiments of the present invention.

Based on the experimental results of Examples 1 and 2, the mechanism ofmicrochemical adsorption is estimated. Since the first compound (e.g.,compounds ImS and AST) having a nitrogen atom-containing cyclicmolecular structure has a large molecular structure, space is formedbetween the molecules when chemically adsorbed. A second compound havinga small molecular weight and having a chain structure (e.g., compoundAAS) can have the effect of entering into the intermolecular spacebetween the first compounds ImS and AST and blocking the space. Thismakes it possible to enhance the chemical adsorption density whentotaling the first compound and the second compound, thus enabling animprovement in bonding strength between the LCP film and the copperfoil.

Examples 3 to 7

In Examples 3 to 7, (A) a peeling test, (B) XPS analysis and (C) anFT-IR test were performed.

(A) Peeling Test

A relationship between the mixing ratio of the compounds AST and AAS andthe bonding strength used in Example 2 was examined.

In the aqueous mixed solution containing the first compound (compoundAST) and the second compound (AAS), the total molar concentration of ASTand AAS was fixed at 48 mmol/L and each concentration of AST and AAS waschanged in terms of a molar ratio in a range of 1:0 to 1:15 (2:0 toabout 0.1:1.0 in terms of a ratio of % by weight). The molarconcentration was fixed to a given value since it is possible toproperly compare properties of the compounds by comparing with thenumber of molecules in the solution. That is, by defining the molarconcentration, it is possible to properly compare a relationship betweenthe chemical adsorptivity of each molecule and the bonding strength.

The test piece (double-sided copper clad laminate) used in the peelingtest was formed in the same manner as in Example 1.

Details of compositely addition and measurement results of the peelingstrength are shown in Table 9.

TABLE 9 Comparative Example Example Example Example Example ComparativeExample 4 3 4 5 6 7 Example 5 AST:AAS mmol/L 1:0 1:0.5 1:1 1:2 1:10 1:150:1 AST % by weight 2 1.33 1.00 0.67 0.18 0.13 — mmol/L 48  32 24 16 4.43 — AAS % by weight — 0.36 0.53 0.71 0.97 1.01 1.07 mmol/L — 16 24 3243.6 45 48 Total % by weight 2 1.69 1.53 1.38 1.15 1.14 1.07 mmol/L 48 48 48 48 48 48 48 Peeling strength kN/m 0.60/0.65 0.63/0.67 0.69/0.710.68/0.74 0.70/0.73 0.55/0.61 0.42/0.47 (minimum value/maximum value)

Like Comparative Example 4, when a test piece was formed using anaqueous solution containing only the compound AST, the minimum value andthe maximum value of the peeling strength were 0.60 kN/m and 0.65 kN/m,respectively. When a test piece is formed using an aqueous mixedsolution of the compound AST and the compound AAS by substituting a partof the compound AST with AAS, the peel strength tends to be improved.For example, in Examples 3 to 6, the minimum value of the peel strengthis 0.63 to 0.70 kN/m and the maximum value is 0.67 to 0.73 kN/m. InExample 6 in which the peeling strength is the highest, the maximumvalue of the peeling strength was about 1.12 times (0.73/0.65) that ofComparative Example 4.

The minimum value and the maximum value of the peeling strength ofExample 7 were 0.55 kN/m and 0.61 kN/m, respectively, which were lowerthan those of Comparative Example 4, but were higher than those ofComparative Example 5 (using an aqueous solution containing only AAS)(the minimum value is 0.42 kN/m and the maximum value is 0.47 kN/m).

It has been found that the peeling strength can be improved as comparedwith the case of containing only the second compound (AAS) (ComparativeExample 5) by adding both the first compound (AST) and the secondcompound (AAS) to the aqueous compound solution (Examples 3 to 7). Ithas been found that the peeling strength can be improved as comparedwith the case of containing only the first compound (AST) (ComparativeExample 4) by particularly adding the first compound (AST) and thesecond compound (AAS) at a predetermined ratio (AST: AAS=1:0.5 to 1:10)(Examples 3 to 6).

It is particularly preferable that a molar ratio of the first compound(AST) to the second compound (AAS) is 1:1 to 1:10 (Examples 4 to 6), andthe maximum value of the tensile strength becomes 0.70 kN/m or more,which could not be achieved by a conventional compound, thus making itpossible to achieve extremely strong bonding strength.

(B) XPS Analysis

A relationship between the mixing ratio of the first compound (AST) tothe second compound (AAS) and the state of chemical adsorption of thecompound on the copper foil surface was examined.

An aqueous mixed solution containing the first compound (compound AST)and the second compound (AAS) was applied on a surface of the copperfoil piece. The aqueous mixed solution to be used are the same as thoseused in Examples 3 to 6 and Comparative Examples 4 and 5 (see Table 9).

Any one of aqueous solutions is applied to the surface (both surfaces)of the copper foil piece using a dip coater manufactured by JSP Co.,Ltd. Thereafter, the copper foil piece was heat-treated at 100° C. for 5minutes to form a compound layer on the surface of the copper foilpiece, and the surface of the copper foil piece coated with the compoundlayer was subjected to XPS analysis. XPS spectra of each copper foilpiece are shown in FIGS. 7 to 12.

In order to investigate chemical adsorption of the compound on thecopper foil surface, the XPS spectrum was analyzed mainly with respectto the Cu 2p orbital peak of the XPS spectrum. Regarding the Cu 2porbital peak, a Cu—N bond peak, a Cu—O bond peak and a Cu (0-valent)peak are mainly observed. In FIGS. 7 to 12, the Cu—N bond peak islabeled as “Cu—N”, the Cu—O bond peak is labeled as “Cu—O”, and the Cu(0-valent) peak is labeled as “Cu(0)”.

Each peak is interpreted as follows.

(i) The Cu—N bond peak indicates that the triazine ring and the aminogroup (both are derived from AST) in the compound layer are chemicallyadsorbed on the copper foil surface.(ii) The Cu—O bond peak indicates that the silanol group (derived fromAST) in the compound layer is chemically adsorbed on the copper foilsurface.(iii) The Cu (0-valent) peak indicates that the copper foil surface, onwhich the compound is not chemically adsorbed, is present.

FIG. 7 is an XPS spectrum of a copper foil piece having a compound layerformed by the aqueous AST solution (see Table 9) used in ComparativeExample 4. As a result of detailed analysis of the Cu 2p orbital peak, aslightly small Cu—O bond peak was observed, in addition to the main Cu—Nbond peak (Table 5). The Cu (0-valent) peak was not observed since itwas hidden by noise.

The silanol group indicated by the Cu—O bond peak is a functional groupcontributing to chemical adsorption with the ester structure containedin LCP, PET and the like. Therefore, in order to improve the peelingstrength between the copper foil and the resin film having an esterstructure, the silanol group chemically adsorbed on the copper foilsurface (i.e., silanol group to be consumed) preferably exists in asmall proportion. That is, in the XPS spectrum, it is preferable that noCu—O bond peak is observed (or the peak is as small as possible).

FIG. 8 is an XPS spectrum of a copper foil piece having a compound layerformed by the aqueous AAS solution (see Table 9) used in ComparativeExample 5. As a result of detailed analysis of the Cu 2p orbital peak ofthe XPS spectrum of FIG. 8, like the XPS spectrum (coated with AST) ofFIG. 7, a Cu (0-valent) peak was observed, in addition to the Cu—N bondpeak and a slightly small Cu—O bond peak.

FIGS. 9 to 11 are XPS spectra of a copper foil piece having a compoundlayer formed by the aqueous mixed solution of AST and AAS (see Table 9)used in Examples 3 to 5.

In FIG. 9, a molar ratio of AST to AAS in the aqueous mixed solutionused is 1:0.5. In FIG. 10, a molar ratio is 1:1. In FIG. 11, a molarratio is 1:2. In the XPS spectrum of FIGS. 9 to 11, a main Cu—N bondpeak, a Cu—O bond peak and a Cu (0-valent) peak were observed. In XPSspectra thereof, each peak intensity of the Cu—O bond peak and the Cu(0-valent) peak is larger than that in FIGS. 7 and 8, and becomes closerto the peak intensity of the Cu—N bond peak. That is, by mixing AAS withAST, it becomes possible to observe the Cu (0-valent) peak, which wasnot observed in FIG. 7 (AST alone), and the peak intensity of the Cu—Obond peak increased to the same level as that of the Cu—N bond peak.

These results revealed the following tendency when the molar ratio ofAST to AAS in the aqueous mixed solution is 1:0.5 to 1:2.

Since the peak intensity of the Cu (0-valent) peak increases, thedensity of chemical adsorption of the compound on the surface of thecopper foil decreases.

Since the peak intensity of the Cu—O bond peak increases, it isconsidered that a large amount of silanol groups are chemically adsorbedon the surface of the copper foil, where a large amount of silanolgroups are consumed. As mentioned above, since the silanol group ischemically adsorbed to the ester structure of the resin film, it is notpreferable that the silanol group is consumed on the surface of thecopper foil.

These results can be regarded as a state where the effect of adding AASto AST is not sufficiently exerted from the viewpoint of chemicaladsorption of the compound on the copper foil surface.

As a result of analyzing the Cu 2p spectrum in more detail, the peakintensity of the Cu—O bond peak and that of the Cu (0-valent) peak arealmost the same in FIG. 9 (a molar ratio of AST and AAS is 1:0.5). InFIG. 10 (a molar ratio is 1:1), the peak intensity of the Cu (0-valent)peak is larger than that of the Cu—O bond peak. In FIG. 11 (a molarratio is 1:2), the peak height of the Cu (0-valent) peak became slightlylower than that of the Cu—O bond peak. It has been found that a changein molar ratio of AST and AAS in the aqueous mixed solution leads to achange in peak intensity of the Cu (0-valent) peak and the Cu—O bondpeak, thus changing the state of chemical adsorption of the compound onthe copper foil surface.

FIG. 12 is an XPS spectrum of a copper foil piece having a compoundlayer formed by an aqueous mixed solution of AST and AAS (see Table 9)used in Example 6. A molar ratio of AST to AAS in the mixed aqueoussolution used is 1:10.

In FIG. 12, the peak intensity of Cu—O and Cu (0-valent) significantlybecame lower than that of the Cu—N bond peak, and the Cu (0-valent) peakmostly disappeared. Since the peak of Cu (0-valent) has mostlydisappeared, it is judged that the copper foil surface is substantiallycoated with the compound layer. It can be seen that, since the Cu—O bondpeak remarkably decreased, the silanol group, which is not chemicallyadsorbed on the copper foil surface, exists in a high proportion. Thatis, a large amount of silanol groups, which can be chemically adsorbedto the ester structure of the resin film, remain.

If the ratio of AAS is further increased, it becomes impossible toobtain the effect of mixing AST and AAS. For example, as shown in Table9, since the ratio of AAS in the aqueous mixed solution is too high (amolar ratio of AST and AAS is 1:15) in Example 7, the peeling strengthremarkably decreased. It is considered that the effect dependsexclusively on AAS.

The results of (A) peeling test and (B) XPS analysis (Table 9 and FIGS.9 to 12) revealed that the effect of improving the peeling strength wasobtained when the molar ratio of AST and AAS in the aqueous mixedsolution is in a range of 1:0.5 to 1:15, and the effect becomes maximumwhen the molar ratio is especially 1:10.

It was thus confirmed that a compound layer having a high bondingstrength can be formed by mixing the first compound having a bulkycyclic structure with the second compound having a linear structure. Itwas also confirmed that it becomes possible to particularly effectivelyutilize a difference in three-dimensional structure between the bulkycyclic structure compound and the linear compound by appropriatelyadjusting the mixing ratio of these compounds, thus making it possibleto optimize the density and structure of chemical adsorption of thecompound to the copper foil and the resin film having an esterstructure.

In other words, in order to exert the effects of the invention accordingto the present disclosure to the utmost, it is important to not only mixa plurality of widely used linear silane coupling agents and/or to mix aplurality of bulky compounds, but also to select the compound and toappropriately adjust the mixing ratio.

(C) FT-IR Analysis

The bonding state between the compound layer and the surface of the LCPfilm was examined.

In the same manner as in the above “(A) peeling test”, test pieces(both-side copper clad laminates) of Comparative Examples 4 and 5 andExample 6 were prepared. The obtained copper clad laminate was immersedin an aqueous 30 to 35% ferric chloride solution at a temperature of 60°C. for 5 to 6 minutes to dissolve and remove (wet etching) the copperfoil. Thereby, the compound layer formed between the copper foil and theLPC film piece was exposed. After washing with ion exchanged water anddrying in an oven at 80° C. for 30 minutes, an LPC test piece (LPC filmpiece coated with a compound layer) for FT-IR analysis was obtained.

With respect to the LPC test piece for measurement, the surface coatedwith the compound layer was analyzed by FT-IR. FT-IR analysis wasperformed by the attenuated total reflection (ATR) method using Fouriertransform infrared spectrophotometer FT/IR680 Plus manufactured by JASCOCorporation attached with multiple total reflection measuring apparatusATR500/M manufactured by JASCO Corporation. Using a Ge prism for themultiple total reflection measuring apparatus, measurement was performedat an incident angle of 45° and a reflection number of 5 times. An FT-IRchart of each LPC test piece is shown in FIGS. 13 to 15.

FIG. 13 is an FT-IR chart of the LPC test piece made from the copperclad laminate of Comparative Example 4. A peak (weak broad) of the C—Ngroup of the triazine ring of AST was detected at 3,383 cm⁻¹, a peak ofthe CH₂ group peak (weak) was detected at 2,962 cm⁻¹ and 2,926 cm⁻¹, apeak of the C═O group of the ester group of the LCP film A was detectedat 1,735 cm⁻¹, and a peak of the Si—OH group of AST was detected at 914cm⁻¹.

FIG. 14 is an FT-IR chart of the LPC test piece made from the copperclad laminate of Comparative Example 5. A peak (weak) of the CH₂ groupof AAS was detected at 2,926 cm⁻¹, a peak of the C═O group of the estergroup of the LCP film was detected at 1,735 cm⁻¹, and a peak of theSi—OH group of AAS was detected at 914 cm⁻¹.

FIG. 15 is an FT-IR chart of the LPC test piece made from the copperclad laminate of Example 6. The FT-IR chart of FIG. 15 is largelydifferent from those of FIGS. 13 and 14. A peak of the C—N group of thetriazine ring of AST was detected at 3,295 cm⁻¹ and a peak of the CH₂group at 2,966 cm⁻¹ and 2,926 cm⁻¹ are stronger than those of FIGS. 13and 14. Meanwhile, the peak of the C═O group of the ester group of theLCP film at 1,735 cm⁻¹ is weaker than those in FIGS. 13 and 14. A peakof the C═N group of the triazine ring of AST appeared newly at 1,715cm⁻¹. Like FIGS. 13 and 14, a peak of the Si—OH group was detected at920 cm⁻¹.

A consideration is made of the results of FT-IR of FIGS. 13 to 15.

The inventors of the present invention have found that the results ofFT-IR are consistent with the results of the peeling test of the copperclad laminate (see Table 9) by interpreting the results of FT-IR asfollows. That is, by interpreting as follows, it is possible tologically explain that the peeling strength of each Example is higherthan that of each Comparative Example. It is noted that, even if thefollowing interpretation does not match the actual phenomenon, theeffects of the invention according to the present disclosure are notdenied.

In Comparative Examples 4 and 5, the peeling strength between the copperfoil and the LCP film is weak (see Table 9). This is due to insufficientformation of bond between the compound (AST or AAS) and the substrate,especially formation of bond between the compound and the esterstructure of the LCP film. Therefore, when the copper foil waswet-etched to prepare an LPC test piece for FT-IR analysis, a part ofthe compound layer disposed between the copper foil and the LCP film wasremoved. That is, in the LPC test piece, the surface of the LCP film waspartially exposed from the compound layer. As a result, a peak of theC═O group of the ester group of the LCP film at 1,735 cm⁻¹ appearedlargely in the FT-IR chart of FIGS. 13 and 14.

Meanwhile, in Example 6, since an aqueous mixed solution of AST and AASwas used, a sufficient bond (high-density bond) was formed between thecompound and the ester structure of the LCP film. Therefore, when thecopper foil was wet-etched, the compound was not removed. That is, theLPC test piece was coated with the compound layer. As a result, in theFT-IR chart of FIG. 15, a peak of the C═O group of the ester group ofthe LCP film at 1,735 cm⁻¹ became smaller. A peak of the C═N group ofthe triazine ring of AST at 1,715 cm⁻¹ appeared clearly (this peak didnot appear in Comparative Example 4 (FIG. 13) using AST). As comparedwith the FT-IR chart of FIGS. 13 and 14, in the FT-IR chart of FIG. 15,a peak of the C—N group of the triazine ring of AST at 3,295 cm⁻¹derived from the compound and peaks at 2,966 cm⁻¹ and 2,926 cm⁻¹ of theCH₂ group became stronger.

The results of (C) FT-IR analysis (FIGS. 13 to 15) revealed that thepeel strength of the copper clad laminate is estimated in the copperclad laminate produced by bonding the copper foil piece and the LCP filmpiece to each other through the compound layer interposed therebetween.It was also found that it is possible to specify or estimate the type(one or plural types) of the compound that forms the compound layer byexamining the position and intensity of the peak of the FT-IR chart indetail.

As mentioned above, it was possible to firmly bond the copper metalsubstrate and the polyester-based resin member to each other bycompositely adding alkane type amine-based silane coupling agents to thecompound having a nitrogen atom-containing cyclic molecular structure.

This application claims priority based on Japanese Patent ApplicationNo. 2016-013477 filed on Jan. 27, 2016, the disclosure of which isincorporated by reference herein.

DESCRIPTION OF REFERENCE NUMERALS

-   -   3 Copper alloy article    -   10 Copper alloy substrate    -   15 Copper alloy member    -   20 Compound layer    -   40 Polyester-based resin body    -   47 Polyester-based resin member    -   50 Hydrogen peroxide solution

1. A polyester-based resin member comprising: a polyester-based resinbody; and a compound layer provided on a surface of the polyester-basedresin body for bonding a substrate made of a copper alloy and thepolyester-based resin body, wherein the compound layer consists of; (a)a first compound which is a compound having a nitrogen-containingfunctional group and a silanol group, and (b) a second compound which isan alkane type amine-based silane coupling agent, wherein the firstcompound is selected from the group consisting of2-(3-Triethoxysilylpropyl)amino-4,6-di(2-aminoethyl)amino-1,3,5-triazine(AST), Imidazole-based silane compound (ImS), AST analogous compoundsand imidazole silane coupling agents, wherein the AST analogouscompounds is selected from the group consisting of compounds in which atriethoxy group of AST is substituted with a trimethoxy group, andcompounds in which an amino substituent of a 4,6-di(2-aminoethyl)aminogroup of AST is substituted with an N-2-(aminoethyl)-3-aminopropylgroup, a 3-aminopropyl group, an N-(1,3-dimethyl-methylidyne)propylaminogroup, an N-phenyl-3-aminopropyl group, anN-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group or a 3-ureidopropylgroup, wherein the imidazole silane coupling agents is selected from thegroup consisting of compounds having any one of a 1-imidazolyl group, a3-imidazolyl group and a 4-imidazolyl group, together with atrialkoxysilyl group.
 2. The polyester-based resin member according toclaim 1, wherein the polyester-based resin body is made of apolyester-based resin selected from the group consisting of polyethyleneterephthalate, polymethylene terephthalate, polybutylene terephthalate,polyethylene naphthalate, polybutylene naphthalate and a liquid crystalpolymer.
 3. The polyester-based resin member according to claim 1,wherein the first compound is AST or AST analogous compounds.
 4. Amethod for producing a polyester-based resin member comprising; apolyester-based resin body, and a compound layer provided on a surfaceof the polyester-based resin body for bonding a substrate made of acopper alloy and the polyester-based resin body, the method comprising:bringing a solution into contact with a surface of the polyester-basedresin body, the solution containing; a first compound which is acompound having a nitrogen-containing functional group and a silanolgroup, and a second compound which is an alkane type amine-based silanecoupling agent, and then heat-treating the polyester-based resin body,wherein the first compound is selected from the group consisting of2-(3-Triethoxysilylpropyl)amino-4,6-di(2-aminoethyl)amino-1,3,5-triazine(AST), Imidazole-based silane compound (ImS), AST analogous compoundsand imidazole silane coupling agents, wherein the AST analogouscompounds is selected from the group consisting of compounds in which atriethoxy group of AST is substituted with a trimethoxy group, andcompounds in which an amino substituent of a 4,6-di(2-aminoethyl)aminogroup of AST is substituted with an N-2-(aminoethyl)-3-aminopropylgroup, a 3-aminopropyl group, an N-(1,3-dimethyl-methylidyne)propylaminogroup, an N-phenyl-3-aminopropyl group, anN-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group or a 3-ureidopropylgroup, wherein the imidazole silane coupling agents is selected from thegroup consisting of compounds having any one of a 1-imidazolyl group, a3-imidazolyl group and a 4-imidazolyl group, together with atrialkoxysilyl group, wherein the compound layer consists of the firstcompound and the second compound.
 5. The method according to claim 4,wherein a molar concentration ratio of the first compound to the secondcompound in the solution is 1:0.5 to 1:15.
 6. The method according toclaim 4, wherein the first compound is AST or AST analogous compounds.